多壁碳纳米管结构对复合光催化剂催化效果的影响

采用溶胶凝胶法制备了多壁碳纳米管负载纳米TiO₂的复合光催化剂（TiO₂/MWCNTs）,以偶氮类染料甲基橙为目标污染物,在自制的光催化反应器上进行了光催化降解反应实验。主要研究同一甲基橙初始浓度（C₀)下,多壁碳纳米管不同管长和管径对复合光催化剂催化效果的影响。结果表明：该降解反应可用一级反应动力学方程描述,反应速率常数k随着多壁碳纳米管管长和管径的增大而增大;与纯纳米TiO₂相比,复合光催化剂对甲基橙的降解率提高了6％～18％,反应速率常数为前者的1.19～2.11倍;采用复合光催化剂的甲基橙光降解溶液自行沉降分离效果较好,静止沉降60 min后达到沉降平衡,剩余浊度为8.5 NTU,下降了90.6％。     

沸石负载Cu_2O光催化剂降解甲基橙

采用化学沉积法,以Cu SO4·5H2O和Na2SO3为原料,以人造沸石为载体,在HAC-Na AC缓冲溶液中制备了沸石-Cu2O复合型光催化剂。在仿日光光源照射下,分别从降解时间、甲基橙初始浓度及初始p H、降解温度等不同方面考察了对复合光催化剂降解甲基橙的影响。结果表明,当甲基橙初始浓度为25 mg/L、初始p H在7.00~10.00之间,降解温度为40℃,复合型光催化剂对甲基橙的降解效果最好;样品重复性使用实验表明,沸石-Cu2O复合光催化剂在可见光区具有良好的光催化活性和稳定性;离子干扰实验证明,Cl-浓度控制在1.2 g/L之内时对甲基橙降解效果影响较小。     

石墨烯/TiO_2复合物的制备及其光催化性能

为拓展二氧化钛(TiO_2)在可见光区的光响应范围,在140℃水热条件下制备了不同氧化石墨烯含量的石墨烯/二氧化钛(RGO/TiO_2)复合材料。利用X-射线粉末衍射仪(XRD)、扫描电子显微镜(SEM)等对材料进行了表征。以甲基橙为目标污染物,研究了在模拟太阳光和紫外光照下TiO_2和RGO/TiO_2对甲基橙的光催化降解性能。结果表明,TiO_2和GO复合后,TiO_2由原来单一的金红石型转变为金红石型和锐钛矿型并存,出现了混晶效应;在模拟太阳光的条件下,复合材料的催化活性均高于TiO_2本身;光照4 h后80 mg氧化石墨烯添加量制备的复合材料对甲基橙的光催化降解率达到69.58%,是TiO_2的1.65倍;在紫外光照1.5 h时,复合材料对甲基橙的降解率达到了70%。由此可知,石墨烯的存在能够促进TiO_2半导体中电子和空穴的有效分离,显著提高了TiO_2光催化剂对可见光的响应。     

不同有机分子修饰对二氧化钛光降解甲基橙的影响

采用改进的溶胶-凝胶法制备了不同有机分子修饰的纳米TiO_2粉体材料。利用X射线粉末衍射(XRD)、红外光谱(FT-IR)、高分辨率的透射电镜(HRTEM)对有机分子修饰的TiO_2进行分析表征。结果表明,制备的纳米TiO_2粉体粒径均匀,表面修饰效果较好,完全为锐钛矿型。通过甲基橙溶液光降解实验,比较了不同有机分子修饰的TiO_2粉体的光降解性能,实验发现有机分子修饰的纳米TiO_2吸附甲基橙达到平衡所需要的时间远大于P25吸附平衡时间,修饰的有机分子均能提高催化剂的光催化活性,胺类有机分子修饰的TiO_2光降解甲基橙的效能要比酸类有机分子修饰的TiO_2光降解甲基橙的效能好,其次有机分子链长也有一定的影响。     

二氧化钛固定化负载及其光催化性能

利用溶胶-凝胶法及浸提技术,进行二氧化钛的固定化负载.通过XRD和SEM对其物相和微观形貌进行分析;利用甲基橙为目标污染物,探究制备以及催化工艺对二氧化钛催化降解性能的影响及其重复使用效果.结果表明,随着浸涂次数的增加,不锈钢丝网表面二氧化钛薄膜的微观形貌有所变化,对甲基橙的光催化降解效率呈现先增大后减少的趋势.浸提7次所制备的二氧化钛光催化降解效率最高,搅拌条件下的4h紫外光降解率可达77.6％.     

负载工艺对ACF担载二氧化钛光催化性能的影响

采用分散液中添加环氧树脂黏结剂并进行热处理的方法,制备出活性炭纤维(ACF)担载二氧化钛光催化材料。并对光催化材料的表面形貌和孔结构进行表征,评价复合光催化材料对亚甲基蓝溶液的光催化降解性能。重点探讨了负载方式、负载时间以及光催化剂的添加量等方面对光催化活性的影响。研究表明,当采用浸渍方式、负载时间控制在15 min左右、光催化剂添加量达11 g/L时,ACF/TiO2光催化复合材料中光催化剂负载量最佳,在15%左右,对亚甲基蓝(初始浓度为50 mg/L)的降解效果最好,在2 h内可以达到90%。     

磷钨酸光催化降解甲基橙溶液的研究

以磷钨酸为光催化剂,在紫外灯照射下,对模拟染料废水甲基橙溶液进行光催化降解,并研究了催化剂加入量、pH值、甲基橙初始浓度和外加氧化剂H2O2对光催化降解效果的影响.结果表明,磷钨酸光催化剂加入量为300 mg/100 mL,pH=2.5时,甲基橙溶液的降解率明显高于其他pH值的降解率;在较低浓度下,甲基橙溶液的光催化降解反应符合一级动力学方程;外加氧化剂H2O2可提高光催化反应速率.     

异质结光催化剂SnS_2/g-C_3N_4的光催化性能研究

以尿素为前驱体,采用热解法合成了石墨相g-C_3N_4;以SnCl_4·5H_2O和硫代乙酰胺为前驱体,采用水热法合成超薄六边形SnS_2纳米片。再将SnS_2与g-C_3N_4以不同质量比复合,采用简便的超声分散法制备了超薄的SnS_2/g-C_3N_4异质结光催化剂。采用紫外—可见漫反射光谱(UV—VisDRS)、紫外—可见光谱(UV—Vis)等对其进行了表征。通过甲基橙的可见光催化降解,评价了SnS_2/g-C_3N_4异质结光催化剂的可见光催化活性。当SnS_2与g-C_3N_4质量比为0.05时,SnS_2/g-C_3N_4异质结光催化剂的光催化活性最高,在该条件下,可见光照射1h,甲基橙的光催化脱色率达到48.2%。     

Ag~+-TiO_2/AC复合材料的可见光吸附-光催化协同作用

采用水热法制备活性炭负载银掺杂纳米Ti O2复合材料(Ag+-Ti O2/AC),对样品进行了TEM、XRD、FT-IR和UV-Vis表征,分析了Ag+-Ti O2/AC的微结构、吸收谱特性和掺杂银离子后的半导体带隙变化,并研究了其在可见光下对甲基橙溶液(MO)的降解性能。结果表明,水热法不需要高温处理即可得到高活性的锐钛矿相纳米Ti O2,Ag+掺杂和AC负载均明显提高Ti O2光催化剂的光催化活性,在可见光下光照180 min,0.2 g/L的Ag+-Ti O2/AC对10 mg/L的甲基橙溶液的降解率为73.7%,主要由于存在持续的活性炭局域强吸附-Ti O2光催化降解协同作用,明显提高了甲基橙的降解效率。     

可见光下 H2La2Ti3O10/TiO2光催化降解有机染料的研究

通过固相反应、离子交换、粒子插入等一系列反应合成一种层状纳米光催化复合材料H2La2Ti3O10/TiO2.可见光照射下,对选定的染料模型--甲基橙溶液(20 mg/L)、汽巴克隆黄(100mg/L)、依利尼尔红(100 mg/L)溶液做光降解实验.结果表明,在可见光照射下,H2La2Ti3O10/TiO2均能对溶液中甲基橙、汽巴克隆黄、依利尼尔红有效降解,光照30min后,其对溶液中甲基橙、汽巴克隆黄、依利尼尔红的降解率分别可达60.4%、60.7%和72.0%,而标准TiO2(P-25)仅为6.2%、10.6%和12.3%.     

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)