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。     

盐酸浸出提取赤泥中铝和铁的工艺条件优化

系统研究盐酸浸出赤泥中铝和铁的过程,考察酸浸温度、盐酸浓度、酸浸时间、液固比以及赤泥粒度对铝、铁浸出率的影响。单因素实验和正交实验结果得出,在影响浸出率的酸浸温度、盐酸浓度、酸浸时间和液固比对铁、铝的浸出率的影响几个因素中,酸浸温度和盐酸浓度的影响最大,液固比和浸出时间其次。盐酸酸浸的最佳工艺条件为:赤泥粒度150μm、酸浸温度80℃、盐酸浓度10 mol·L~(-1)、液固比8∶1(V/m)、浸出时间150 min,此时铝的浸出率为96.7%,铁的浸出率为95.1%,铁铝总浸出率96.0%。     

酸浸法提取煤矸石中Al2O3的研究

煤矸石是主要的煤系固体废物,其中Al2O3质量分数约占35％左右.以某煤矿的煤矸石为原料,通过单因素实验比较盐酸和硫酸对Al2O3的浸取率,研究各因素对Al2O3浸取率的影响,确定浸取煤矸石中Al2O3的最佳酸浸介质为硫酸.利用正交实验确定酸浸取的最佳条件为:液固比(酸溶液体积与煤矸石样品质量比)15 mL/g、硫酸摩尔浓度3 mol/L、浸取时间120min、助样比(助溶剂与煤矸石样品质量比)0.20,在此条件下硫酸对煤矸石中A12O3的浸取率可达79.6％.     

煅烧温度和添加剂对提高煤矸石中氧化铝溶出率的实验研究

煤矸石是煤炭在开采、洗选过程中产生的固体废弃物，其中二氧化硅、氧化铝和碳占到矸石总量的90%以上，又是一种可以利用的资源。实验以山西潞安煤矿的洗矸为原料，采用SEM、IR和XRD等分析测试手段对不同煅烧温度下的煤矸石进行微观形貌、化学键变化和矿物组成的分析研究，确定氧化铝的活化温度区间；并根据煤矸石的活化机理，选择提高氧化铝溶出率的添加剂。实验结果为：煤矸石中氧化铝的活化温度区间为600～850℃；酸浸过程中添加氟化钠可以打开煤矸石中的SiO₂—Al₂O₃，使氧化铝溶出率达到90%以上，和通常条件下氧化铝的溶出率相比提高20%左右。本研究为煤矸石高值利用提取氧化铝提供了技术基础，也为粉煤灰等低铝含量矿物的开发利用提供借鉴。     

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。     

盐酸分级浸出赤泥中有价金属元素

采用盐酸2段分级浸出工艺回收氧化铝赤泥中的有价金属元素。通过考察液固比、反应温度、反应时间及盐酸使用量对浸出率的影响,确定了2段浸出的实验工艺。结果表明:在盐酸用量为理论用量的40%、90℃液固比为7∶1、反应时间1 h的条件下,Ca的浸出率为96.2%,Na的浸出率为82.47%,Al的浸出率为42.87%,其他元素几乎不浸出,这是第1段浸出;在盐酸用量为理论量的130%、90℃、盐酸浓度8.8 mol·L~(-1)的条件下,浸出1段酸浸渣,Fe的浸出率99.65%,Sc的浸出率88.76%,V的浸出率93.58%,其他稀土元素的浸出率均达到了70%左右,这是第2段浸出。     

拜耳赤泥中镓的酸法浸出及残渣的除氟

贵州铝土矿资源普遍富含镓元素,拜耳法工艺中,约70%的镓随氧化铝同时溶出,其余30%残存于赤泥中未回收直接外排,造成镓资源的严重浪费。采用酸法工艺浸出拜耳赤泥中镓金属,设计4因素3水平L_9(3~4)正交实验,考察盐酸添加量、浸出温度、浸出时间和液固比对镓浸出效果的交互影响规律,并测试了浸出残渣对含氟水处理性能。结果表明:影响镓浸出率因素的主次顺序依次为盐酸添加量、浸出温度、液固比和浸出时间;最适宜浸出条件为盐酸过量系数1.2,浸出温度70℃,浸出时间3 h,液固比8 m L·g~(-1);该条件下,镓的浸出率为94.92%,浸出溶液含Ga 3.91 mg·L~(-1);除氟实验得出最佳除氟条件为,残渣添加量25 g·L~(-1),p H=4.7,接触时间6 h,旋转速率200 r·min~(-1);室温下进行3组平行实验,平均除氟率为57.54%,表明浸出残渣具有一定的除氟性能。     

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/m L。     

聚合氯化铝铁絮凝剂的制备及其在焦化废水深度处理中的应用

以铝酸钙粉和硫酸亚铁为主要原料,通过酸溶、氧化、聚合和熟化过程制备了无机高分子絮凝剂聚合氯化铝铁,采用正交试验优选出制备聚合氯化铝铁的最佳条件,联合使用聚合氯化铝铁与氧化剂深度处理焦化废水.结果表明,聚合氯化铝铁的最佳制备条件为:硫酸亚铁投加量10 g(以每100 g铝酸钙粉计,下同)、盐酸投加量400 mL、反应温度80℃、反应时间2.5 h;在此条件下制得的絮凝剂氧化铝质量分数为30.5%,全铁质量分数为1.2%.当聚合氯化铝铁投加量为200 mg/L、氧化剂投加量为10 mg/L时,焦化废水中COD去除率可达70%,色度去除率可达63%,出水水质达到<污水综合排放标准>(GB 8978-1996)中的一级排放标准.     

生物沥浸含锰烟粉尘中的锰及其浸出机理研究

含锰烟粉尘是钢铁行业产生的一类含有锰、锌、铅和硅等元素的工业固废，既存在一定的环境风险，又具有潜在的资源回收价值。对含锰烟粉尘分别用生物酸和无机酸进行沥浸，分析锰的浸出机理，进一步通过响应面法确定生物酸沥浸锰的最佳工艺条件。结果表明，锰的浸出机理为酸溶和生物酸还原的复合机理，生物酸中的还原性物质和沥浸过程中产生的Fe²⁺能够将高价锰还原为Mn²⁺,使生物酸体系锰的浸出率比无机酸体系高。生物酸浸出锰的最佳工艺条件：固液比为1.22 g∶100 mL,初始pH为0.81,温度为29.14℃,转速为152.29 r/min,此条件下实际锰浸出率为76.51%。     

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.     

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.     

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.     

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.     

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.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.     

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.