表面活性剂加强动电技术去除污泥中铜和镉

以实际城市污泥为研究对象,通过采用表面活性剂作为阴极液,并考虑阴极液pH值、表面活性剂类型和电压3种因素对动电技术去除污泥中重金属(铜和镉)的影响,选用正交试验确定最佳试验条件.结果表明,采用表明活性剂作为阴极液加强动电技术去除污泥中重金属足可行的,铜和镉的去除率分别达到11.1%～52.6%和9.1%～46.7%.通过对正交试验结果进行极差和方差分析,试验的最佳条件为:电压为20 V,阴极液加入十六烷基三甲基氯化铵并控制pH值为4～6.表面活性剂的类型对动电技术去除镉具有显著影响.其中,表面活性剂类型对动电过程的影响最大,阴极液pH值次之,电压影响最小.     

铅污染土壤电动修复增强技术的研究

利用电动修复技术对铅污染土壤的修复进行了实验室研究,研究了修复时间和络合剂EDTA对电动修复效果的影响,分析了土壤重金属的迁移和变化特征。结果表明,在电场力作用下随着修复时间的增长污染物的去除率相应提高,去除率由修复时间5 d时的13%增加到15 d时的20%。以EDTA作为阴极控制液,EDTA可与硝酸铅反应形成溶解态的络合物,提高铅离子的移动性,从而提高修复效果。随着EDTA浓度由0.1 mol/L到0.2 mol/L,Pb的去除率由44.4%提高到61.5%,说明添加络合剂可以提高修复效果。另外,电动修复效果与铅的形态分布有密切关系,交换态和碳酸盐结合态有利于重金属铅的去除。     

EDTA强化电动力学修复重金属复合污染土壤

在自制的电动力学装置中,研究多种重金属复合污染土壤的电动力学修复,通过在阴极添加络合剂EDTA来提高修复效率。实验结果表明,EDTA的引入提高了修复过程中的电流值,且EDTA与重金属的络合提高了污染物向电极液的迁移效率,从而强化了电动力学修复效果。在设定的浓度(0、0.01、0.02、0.05和0.1 mol/L)中,0.1 mol/L的EDTA具有最佳的修复效率。在此实验条件下,污染土壤中的总铜、总铅和总镉的去除率分别为90.2%、68.1%和95.1%。电动力学修复后,对土壤重金属进行化学形态分析,发现电动力学修复显著改变了土壤重金属存在形态,修复后土壤中的铜、铅、镉主要以较稳定的有机态和残余态形式存在,显著降低了对周边生物和环境的毒害。     

柠檬酸强化电动去除和回收污泥中的重金属

探讨了柠檬酸对污泥中重金属形态的影响,并以柠檬酸为络合剂、以杭州七格污水处理厂城市污泥为研究对象,在0.8 m A·cm-2恒定电流密度条件下运行120 h,在5组柠檬酸浓度分别为0.00、0.05、0.10、0.20和0.30 mol·L~(-1)的条件下,采用自行设计的双层双阳极反应器对污泥中重金属进行电动去除和回收实验。结果显示,柠檬酸能促使污泥中大量的Zn由可还原态转化为酸可提取态,但对Cu的形态影响不大。电动处理实验中,添加柠檬酸后Zn和Cu的去除率都有明显提高,当柠檬酸浓度为0.20 mol·L~(-1)时,Zn的去除率最大达58.3%,Cu的去除率为42.4%;当柠檬酸浓度为0.10 mol·L~(-1)时,Cu的去除率最大为51.7%,Zn的去除率为46.4%。柠檬酸的最佳添加浓度为0.10~0.20 mol·L~(-1),当柠檬酸添加量超过0.20 mol·L~(-1),Zn和Cu的去除率反而会因为络合物在阳极区的沉淀而降低。     

Fe~Ⅱ（EDTA）协同生物转鼓过滤器去除NO的实验研究

采用自行研制的生物转鼓反应器（RDB）处理难溶于水的NO废气,为提高NO的传质系数和去除效率,实验考察了营养液中添加FeⅡ（EDTA）络合剂协同RDB以提高NO去除效率的过程。结果表明,当空床停留时间（EBRT）为0.96 min时,在营养液中添加FeⅡ（EDTA）至100 mg/L后,NO的去除效率从70.78%升至79.26%。未添加FeⅡ（EDTA）时NO去除率随营养液的增加下降,添加FeⅡ（EDTA）至100 mg/L后,去除率随营养液量的增加先上升后下降,且下降速率比上升速率大。随着营养液中FeⅡ（EDTA）浓度从0增加至500 mg/L,实验最佳温度从32.5℃升至47.5℃,但添加FeⅡ（ED-TA）至100 mg/L对实验的最适pH值没有太大影响。     

铜污染场地土壤的原位电动强化修复

电动修复技术是一种新型的污染土壤修复技术,相关的理论和实验室小试研究较多,但鲜见野外现场条件下的原位修复研究。本研究以某电镀厂铜污染区为修复对象,以可生物降解的络合剂乳酸和柠檬酸为阴极池增强试剂,考察在原位条件下电动修复技术对土壤中铜的去除效率,并评估修复过程的电能消耗。结果表明:在电压梯度7.5 V·m~(-1),阴极池乳酸和柠檬酸浓度为0.5 mol·L~(-1),处理24 d(乳酸处理)和17 d(柠檬酸处理)的条件下,乳酸处理较柠檬酸处理电流要高、且阴阳极池溶液和土壤的pH、电导率变化要小;乳酸处理后土壤铜含量明显下降(阳极和阴极附近土壤铜去除率分别为52.6%和35.7%),而柠檬酸处理条件下阳极和阴极附近铜的去除效率分别为27.2%和~(-1)7.5%,这可能与其较低的电流和较短的处理时间有关。与现有文献比较,乳酸处理总能耗(15.7 k Wh·m~(-3))处于较低水平,而Cu的去除率处于较高水平(35.7%~52.6%),优于文献报道的电动修复去除效率和电能消耗。     

Cd污染土壤的电动修复及其强化

为了提高电动修复镉污染土壤的效率,通过配制镉污染土壤,搭建电动修复实验装置,研究电场强度、电解液种类和添加膨润土对电动修复镉污染土壤中总Cd去除率的影响。结果表明,电动修复时间120 h,电场强度从2.5 V·cm-1增加至3 V·cm-1时,总Cd去除率增加10.62%,电场强度从3 V·cm-1增加到3.5 V·cm-1时,去除率增加1.87%;与柠檬酸为电解液对比,乙酸的总Cd去除率增加12.14%,总耗能增加62.13%,盐酸的总Cd去除率增加18.04%,总耗能增加了187.9%;乙酸为电解液,阴阳两极电解液循环与不循环相比总Cd去除率增加25.48%,能耗增加13.69%;在靠近阴极、中部及靠近阳极土壤中添加膨润土墙,总Cd去除率分别上升20.89%、18.22%、10.67%,能耗分别降低11.00%、13.43%、13.73%。循环电解液能有效减缓电阻极化和浓差极化现象并提高总镉去除率。电动修复联合膨润土吸附,能提高土壤中的总镉去除率,同时降低能耗。     

利用柠檬酸去除污泥中镉、铅的研究

考察了利用柠檬酸去除厦门某化工厂污泥中重金属镉、铅的适宜工艺条件,包括pH、柠檬酸浓度、转速、温度、反应时间等。考察发现,在pH-3、柠檬酸摩尔浓度为0．2mol／L、转速为200r／min、温度为室温、反应时间为1d左右时,污泥中镉、铅的最大去除率分别为91．5％和96．5％。     

EDTA-（NH4）2FeSO4络合剂脱除烟气中的氮氧化物

络合脱硝法是近年来新型的脱除氮氧化物的方法之一,其中EDTA金属络合剂受到了广泛关注,而亚铁络合剂又具有很好的脱除氮氧化物的效果。考查了硫酸亚铁铵与EDTA形成的Fe（II）EDTA这种比较常见的EDTA金属络合剂对NO的吸收容量,并考查温度、络合剂浓度等对Fe（II）EDTA吸收NO的影响。研究结果表明：在相同的实验环境和实验条件下,对于影响Fe（II）EDTA吸收NO的因素最重要的是温度,其余依次为络合剂浓度、气体流速、氧含量、吸收液pH,最适宜吸收条件是反应温度50℃、络合剂浓度0．1mol／L、进气流速600mL／min、氧含量2％、吸收液pH=6。     

动电修复不同形态重金属污染土壤效果研究

以钢铁厂附近废地的重金属土壤为对象,研究了动电修复技术去除重金属效果与其各化学形态的关系,讨论了电能消耗。结果表明,同一种重金属,其动电去除效率顺序为交换态碳酸盐结合态Fe-Mn氧化结合态有机结合态残留态,即吸附性越弱的形态,其去除率越高,如交换态去除率95%;吸附性越强的形态,其去除率越低,如有机态和残留态去除率低于29%;对于不同重金属,高移动性和弱吸附性的重金属较弱移动性和强吸附性的重金属去除效果好,即各形态的Cd、Cu和Zn的去除率明显高于相应形态Pb的去除率;能耗分析表明,实验时间超过96 h后,在电能有较大消耗的同时,重金属去除率却提高不明显。     

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.     

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.     

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.     

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)