廉价吸附剂处理重金属离子废水的研究进展

随着现代工业的迅速发展，生产过程中排出的有害重金属离子废水日益增加。寻找较为廉价的废水净化材料，对其中有害重金属离子的有效处理已成为环境保护中亟待解决的问题。廉价吸附剂的使用取代了目前成本较高的从溶液中回收重金属离子的方法，同时吸附剂改性会大大提高其吸附量。阐述了壳聚糖、海泡石、膨润土、海藻和泥炭等结构组成、吸附和离子交换性能等，报道廉价吸附剂对一些重金属离子的最大吸附量是：796mgPb／g壳聚糖，1123mgHg／g壳聚糖。92mgcr（Ⅲ）／g壳聚糖，76mgCr（Ⅲ）／g泥炭，41mgPb／g膨润土，558mgCd／g壳聚糖，215mgCd／g海藻。由此展现了廉价吸附剂在重金属离子废水处理过程中的巨大优势和良好的发展前景。     

半焦吸附养殖废水中的重金属

采用生物质半焦作为吸附剂处理养殖废水中的重金属,并对半焦吸附重金属的吸附容量及吸附效率进行了分析和评估。实验结果表明,生物质半焦对养殖废水中Cu、Zn、Pb和Cd 4种重金属具有较好的吸附效果,吸附容量分别为22.4、19.03、17.30和16.94 mg/g,且吸附率均达到70%以上,氮磷的影响吸附不超过30%。重金属离子在半焦表面上的吸附过程符合Langmuir等温吸附模型,且主要为单分子层表面吸附。由此生物质半焦作为廉价高效的吸附剂处理养殖废水中重金属技术上可行,为养殖废水中重金属吸附研究及生物质半焦资源化利用提供新途径。     

聚(丙烯酸-co-丙烯酰胺)/膨润土/腐植酸钠三维网络凝胶吸附剂对Cd2+吸附性能研究

制备了一种聚(丙烯酸-co-丙烯酰胺)/膨润土/腐植酸钠三维网络凝胶吸附剂,重点考察了吸附剂对Cd2+吸附的pH依赖性、吸附动力学和吸附等温线.结果表明,Cd2+溶液pH值对吸附容量有较大影响.在pH=8、吸附时间30 min、Cd2+溶液初始浓度0.02 mol/L和吸附剂用量0.10 g的条件下,吸附剂对Cd2+的饱和吸附量可达294.7 mg/g.与膨润土相比,三维网络凝胶吸附剂具有更高的吸附容量和更快的吸附速率.     

4A沸石对复合污染水体中Pb2+、Cu2+和Cd2+的去除

采用静态吸附法以4A沸石为吸附剂研究其对复合污染水体中Pb2+、Cu2+和Cd2+的竞争吸附特性,并探讨了影响吸附的环境因素。实验表明,在室温条件下,溶液pH5～6,4A沸石15 mg对10 mL复合污染溶液(Pb2+、Cu2+和Cd2+浓度分别为100 mg/L)吸附20 min时,对溶液中3种重金属的吸附去除率均可达99.8%以上。反应过程中4A沸石对3种重金属的吸附速率大小为Pb2+>Cu2+>Cd2+。复合污染水体中4A沸石对Pb2+、Cu2+和Cd2+的吸附符合Langmuir和Fre-undlich等温吸附方程,相关系数分别为0.9981、0.9901、0.9916和0.9638、0.9194、0.9689。经计算,4A沸石对Pb2+、Cu2+和Cd2+的饱和吸附量分别为129.9 mg/g、107.5 mg/g和99.0 mg/g。4A沸石吸附重金属离子达到吸附平衡的时间较短,对溶液pH值的适应性较好。吸附后的4A沸石可以再生利用,对铅离子洗脱重复利用性较铜离子和镉离子强。     

赭石对模拟重金属废水的吸附效果研究

采用模拟重金属废水的正交试验设计，进行赭石对模拟重金属废水的吸附效果研究，探讨pH、赭石加入量和振荡时间等影响因素对吸附效果的影响。结果表明，在一定pH、赭石加入量和振荡时间条件下，赭石对6种重金属（Pb、Cd、Mn、Zn、Cr和Ni）均有较好吸附效果，对Pb、Cd、Mn、Zn和Cr的最大吸附率可达100%，对Ni的吸附率达8963%。处理后废水中重金属达到污水排放标准。各影响因素对Mn、Zn和Cr吸附效率的影响大小表现为：pH＞赭石加入量＞振荡时间，Ni和Cd表现为：赭石加入量＞pH＞振荡时间，Pb表现为：pH＞振荡时间＞赭石加入量。赭石对废水中重金属吸附的最佳条件为赭石加入量40 g/L，pH 10～10.5，振荡时间2 h。     

原位帽封材料对水体中Pb(Ⅱ)与Cd(Ⅱ)静态吸附

用无纺布包裹珊瑚和丙烯酸树脂制成帽封材料,将底泥中重金属离子原位固定的同时吸附水体中的重金属离子pb2和Cd2.通过红外光谱,电镜扫描和火焰原子吸收仪器来分析该帽封材料的吸附性能.通过改变pH值,吸附剂投放量来检测其吸附效果.结果表明,该帽封材料在pH等于5的时候,Cd2最大吸附量达到434.67 mg/g,pb2+最大吸附量达到524.27 mg/g.pH和吸附剂量保持不变,随着底物浓度增加吸附量也增加;电镜扫描图和红外光谱图表明,该材料能很好地吸附重金属离子.     

改性板栗壳CACS对Cr(Ⅲ)的吸附性能

以板栗壳为原料,经过柠檬酸改性后制备成重金属吸附材料CACS,通过考察初始p H值、吸附剂投加量等因素对模拟废水中Cr(Ⅲ)去除率的影响,以及吸附动力学过程和等温吸附特征,分析探讨CACS对水中Cr(Ⅲ)的吸附特性及吸附机理。结果表明,p H为4.0,吸附剂投加量为1 g/L时,CACS对Cr(Ⅲ)的饱和吸附容量达33.4 mg/g;与未改性板栗壳CS相比,吸附容量提高了49.5%;吸附过程符合准二级动力学模型,表明吸附速率受化学吸附控制,吸附等温规律遵从Langmuir模型,表明吸附过程主要是表层吸附;结合吸附前后的扫描电镜(SEM)和傅里叶红外光谱(FTIR)的图谱分析,推断改性板栗壳CACS对Cr(Ⅲ)的吸附存在表面吸附、静电引力、络合和离子交换作用,而羟基和羧基与Cr(Ⅲ)发生配位作用可能是吸附量提高的主要原因。     

膨润土对Pb2+、Cu2+、Cr3+的吸附动力学及等温线研究

研究所用膨润土的主要成分为SiO2和Al2O3,属于Ca基膨润土,BET表面积为50.83 m2/g.在恒温及恒定pH条件下,用静态吸附法研究了膨润土对Pb2 、Cu2 、Cr3 的吸附特性,结果表明其较好地符合Lagergten二级吸附速率方程,对这3种离子的吸附速率为Pb2 ＞Cu2 ＞Cr3 .利用3种等温线方程对吸附过程进行拟合,发现利用Langmuir吸附等温方程计算的值与膨润土吸附Pb2 、Cu2 、Cr3 试验数据最为吻合.膨润土对3种金属离子的平衡吸附量为Cr3 ＞Cu2 ＞Pb2 .     

微波法制备工业污泥含碳吸附剂及其除铬性能

为实现工业集中区污水处理厂的脱水污泥(简称工业污泥)的废物资源化,以工业污泥为原料,通过氯化锌浸渍微波辐射法制备污泥炭吸附剂,探讨了制备过程中不同制备条件对污泥炭吸附剂吸附性能的影响,并用于吸附重金属离子铬。实验结果表明,除了微波功率、辐照时间等主要影响因素外,过滤条件、搅拌时间和盛放介质等因素也会影响污泥炭吸附剂的吸附性能,确定了工业污泥炭吸附剂的最佳制备条件是微波功率490 W,辐照时间10.0 min,氯化锌溶液浓度40%,搅拌时间24 h等,并且再生前后活性炭对含铬废水均有较好的处理效果;活性炭的投加量为1.0 g/L,Cr(Ⅵ)初始浓度和振荡速率分别为50 mg/L和100 r/min时,最佳除铬条件为pH、温度和吸附时间分别为2、室温(25℃)和1.0 h,在此条件下,Cr(Ⅵ)的去除率为98.5%,TCr的去除率为86.1%,从而为工业污泥的资源化提供了一条新途径。     

皂化改性橘子皮生物吸附剂对重金属离子的吸附

以生物废料橘子皮(OP)为原料,经乙醇、氢氧化钠处理,得到改性橘子皮生物吸附剂SOP,将其用于对重金属离子Cu2+、Pb2+、Cd2+、Zn2+和Ni2+的吸附。研究了溶液pH、吸附时间和重金属离子初始浓度对SOP吸附性能的影响。结果表明,重金属离子在生物吸附剂上的吸附速率快,符合准二级动力学方程。SOP对重金属离子的吸附等温线符合Lang-muir模型,根据Langmuir模型计算SOP对Cu2+、Pb2+、Cd2+、Zn2+和Ni2+的饱和吸附量分别为56.82、152.4、66.27、33.90和23.02 mg/g,均高于改性前。常见阳离子的存在对重金属离子吸附的影响较小,改性后的橘子皮生物吸附剂可以再生重复使用4次以上,是性能良好的重金属离子吸附剂。     

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.