稀土系列催化剂对焦化废水的催化湿式氧化

以稀土元素Ce制得催化剂系列，在高温，高压条件下对焦化废水进行催化湿式氧化研究，考察载体，焙烧温度，活性组分的配比对催化剂的催化活性的影响，以及反应温度，氧气分压，反应时间和催化剂用量对氧化过程的影响，设计正交实验确定最佳的工艺参数：反应温度为240℃，氧气分压3.0MPa，催化剂用量30g/L，此时废水的COD法除率达到90％以上。     

催化臭氧氧化降解糖蜜酒精废水的研究

以SnO2为催化剂,研究糖蜜酒精废水在臭氧条件下的氧化降解反应,为糖蜜酒精废水的治理提供一种新的处理方法.研究表明,SnO2加速了臭氧氧化反应,使糖蜜酒精废水的氧化降解加快.影响糖蜜酒精废水氧化降解的主要因素有臭氧流量、废水的初始pH和催化剂用量等.加大臭氧流量及增加催化剂用量,均有利于糖蜜酒精废水的降解.适宜的反应条件是:糖蜜酒精废水的稀释倍数为10倍,臭氧流量为130 mg/h,催化剂用量为2.500 g/L,废水的初始pH为4.25,温度为30 ℃.在该条件下反应60 min,废水的脱色率为60.2%,COD去除率为44.5%.动力学分析表明,单独臭氧氧化降解糖蜜酒精废水和SnO2催化臭氧氧化降解糖蜜酒精废水均为拟一级反应.     

催化湿式氧化法处理糖蜜酒精废液的研究

以非贵金属Cu、Fe、Mn和Ce为主要活性成分和TiO2、-γA l2O3为载体,制备了10种用于催化湿式氧化法处理糖蜜酒精废液的催化剂。考察了载体、焙烧温度、成分配比对催化剂催化活性与稳定性的影响,研究了氧气分压、催化剂投加量、反应温度和反应时间对催化湿式氧化过程的影响规律。结果表明:(1)Fe-Mn/-γA l2O3(3∶1∶1)催化剂是催化湿式氧化法处理糖蜜酒精废液的可选催化剂;(2)适宜的氧气供应量为理论需氧量的3.4~4.6倍,催化剂的投加量以10 g/L为佳;在300℃下反应30 m in或在280℃下反应60 m in,处理水可达到污水综合排放标准GB9878-1996的三级标准。     

催化湿式氧化法处理糖蜜酒精废液的研究

以非贵金属Cu、Fe、Mn和Ce为主要活性成分和TiO2、γ-Al2O3为载体，制备了10种用于催化湿式氧化法处理糖蜜酒精废液的催化剂。考察了载体、焙烧温度、成分配比对催化剂催化活性与稳定性的影响，研究了氧气分压、催化剂投加量、反应温度和反应时间对催化湿式氧化过程的影响规律。结果表明：（1）Fe-Mn／γ-Al2O3（3：1：1）催化剂是催化湿式氧化法处理糖蜜酒精废液的可选催化剂；（2）适宜的氧气供应量为理论需氧量的3．4～4．6倍。催化剂的投加量以10g／L为佳；在300℃下反应30min或在280℃下反应60min,处理水可达到污水综合排放标准GB9878—1996的三级标准。     

H2O2处理酸性大红GR染料废水的研究

通过对废水pH值、H2O2用量、催化剂用量、反应时间、反应温度等工艺条件的考察,确定了H2O2催化氧化处理酸性大红染料废水的最佳工艺条件pH 4、H2O2用量6 mL/L、催化剂用量3 g/L、反应时间100 min、反应温度70℃.在该条件下,COD和色度的去除率分别为76.7%和99.4%;通过反应前后的紫外-可见光光谱分析表明,H2O2催化氧化处理酸性大红GR染料废水有比较好的效果,为该工艺处理酸性大红GR染料废水提供了科学依据.     

催化湿式氧化吡虫啉农药废水催化剂的研究

通过共沉淀法制备了用于湿式氧化吡虫啉农药废水的Cu/Mn复合氧化物催化剂,研究了沉淀剂种类、沉淀温度、焙烧温度和活性组分配比等因素等对Cu/Mn复合氧化物催化剂的活性及稳定性的影响,确定了最佳制备条件,利用BET比表面积测定和XRD对催化剂进行了表征.结果表明,优化条件制备的Cu/Mn复合氧化物催化剂催化湿式氧化处理吡虫啉农药废水时,具有较高的催化活性和稳定性.催化剂用量4 g/L,反应温度190℃,氧分压1.6 MPa,反应120 min,COD去除率为92.3%,活性组分溶出量较小.     

H2O2处理酸性大红GR染料废水的研究

通过对废水pH值、H2O2用量、催化剂用量、反应时间、反应温度等工艺条件的考察，确定了H2O2催化氧化处理酸性大红染料废水的最佳工艺条件：pH4、H2O2用量6mL／L、催化剂用量3g／L、反应时间100min、反应温度70℃。在该条件下，c0D和色度的去除率分别为76．7％和99．4％；通过反应前后的紫外一可见光光谱分析表明，H2O2催化氧化处理酸性大红GR染料废水有比较好的效果，为该工艺处理酸性大红GR染料废水提供了科学依据。     

催化湿式氧化技术处理山梨酸生产废水的研究

采用催化湿式氧化技术处理生产山梨酸过程中产生的高浓度有机废水,对催化剂组分进行优选.对反应温度、O2分压(Po2)和废水pH等工艺条件进行考察.实验结果表明:采用自制CuO-Cr2O3-La2O3/TiO2为复合催化剂处理该有机废水时表现出较好的催化活性;在190℃、Po2=2.1 MPa、pH=6.1、COD=10 030.0 mg/L时,反应90 min的COD去除率达到98.3%,而在相同条件下未加催化剂的湿式氧化的COD去除率只有60.1%.     

催化湿式氧化法处理吡虫啉农药废水的优化工艺条件

采用催化湿式氧化技术在2 L高压反应釜中处理吡虫啉农药废水,分别以复合金属氧化物Cu/Mn、Cu/Ce、Ce/Mn及Ce/Ag为催化剂来考察对废水COD去除率的影响.发现Cu/Ce、Ce/Mn、Cu/Mn催化剂有较高的催化活性;Ce/Mn催化剂最稳定;Ce/Ag催化剂的Ag溶出量很大.选用性能良好的Ce/Mn催化剂,考察了反应温度、反应压力和废水的初始pH对催化湿式氧化效果的影响.结果表明,催化剂的加入可使COD去除率提高37%左右,同时处理后废水的BOD5/COD从0.19提高到0.65以上;当反应温度为150～230 ℃时,处理效率随温度升高明显增加;总压4.8 MPa、氧分压1.2～2.4 MPa时,适当增加氧分压亦能提高氧化效率;废水初始pH对氧化效果影响不大,但对催化剂的稳定性有影响.优化工艺条件最终为:催化剂为Ce/Mn;温度190 ℃;氧分压1.6 MPa;进水pH为6.21;反应时间120 min.     

陶瓷-活性炭球为载体的CWAO催化剂

以陶瓷-活性炭球为载体制备载Ru催化剂,用于催化湿式氧化(CWAO)法处理酚醛树脂废水,考察了陶瓷-活性炭球载体、Ru负载量和陶瓷球宏孔孔径等对催化剂的催化活性和稳定性的影响。实验结果表明,催化剂催化活性的顺序为:Ru/KC-120>Ru/KC-80>Ru/KC-60>KC-120>无催化剂。在200℃,氧气分压为1.5 MPa等条件下,催化湿式氧化酚醛树脂废水,3% Ru/KC-120催化剂表现良好的催化活性与稳定性,在120 min内,COD和苯酚去除率分别达到91%和96%。     

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)