负载型TiO2膜太阳光光催化降解活性深蓝K-R的研究

采用抛物线槽型反应装置,研究了玻璃弹簧和微珠负载型TiO2膜太阳光催化降解活性深蓝K-R,结果表明,由于玻璃弹簧具有良好的光透距离,脱色性能显著优于玻璃微珠,玻璃弹簧为载体,水溶液浓度为15 mg/L,pH为3,流速为20 mL/s,太阳光强度在1200 μW/cm2以上,光降解6 h时,脱色率达到96%;该降解反应可用一级反应动力学方程进行描述,反应速率常数(K)与光强I的关系为:K∝I1.92.     

镧负载改性TiO2太阳光催化降解微囊藻毒素的研究

考察了镧负载改性TiO₂催化剂在太阳光下降解微囊藻毒素LR (MCLR)的效果及其影响因素。结果表明,镧负载改性的TiO₂可显著增加MCLR在TiO₂表面的吸附量,同时提高MCLR在太阳光下的降解率。随着镧负载量的增加,太阳光下MCLR降解率可从65%提高到95%,pH降低可促进MCLR的降解。改性TiO₂对藻毒素的降解存在最佳投加量,实验结果表明,在pH=6,MCLR初始浓度为2 mg/L,0.001-La-TiO₂的最佳投量为0.5 g/L,在3 600 μW/cm²太阳光下照射30 min,降解率可达97%。     

光助Ce-Fe/Al2O3催化H2O2降解阳离子红GTL模拟废水

利用Ce-Fe/Al₂O₃为催化剂的非均相光Fenton体系降解阳离子红GTL模拟废水，考察了H₂O₂浓度、催化剂用量、初始pH值及不同工艺过程对降解效果的影响，通过紫外-可见漫反射光谱、红外光谱、XPS手段研究铁在反应中的价态变化。结果表明，在11 W低压汞灯照射下，非均相光Fenton体系能够有效地降解结构稳定的阳离子红GTL，在pH 6，反应温度20℃，时间90 min，Ce-Fe/Al₂O₃ 2 g/L，H₂O₂浓度340 mg/L，含50 mg/L阳离子红GTL模拟废水TOC去除率为92.40%；光Fenton反应中Fe(Ⅲ)转化为Fe(Ⅱ)。     

H4SiW12O40/TiO2/beads光催化降解亚甲基蓝的研究

以钛酸四丁酯为原料,空心微珠为载体,采用溶胶凝胶法制备TiO₂/beads光催化剂载体,然后浸渍法制备出H₄SiW₁₂O₄₀/TiO₂/beads表面负载修饰型复合光催化剂,并运用SEM、XRD、FT-IR和DRS对催化剂进行表征和分析。研究了H₄SiW₁₂O₄₀/TiO₂/beads对亚甲基蓝降解的光催化活性,考察了光强度、pH值、曝气量、底物浓度和催化剂用量等对催化效率的影响。实验结果表明,在中性条件下,H₄SiW₁₂O₄₀/TiO₂/beads催化剂的投加量为0.25 g/L,浓度为7.5 mg/L的亚甲基蓝溶液在250 W的紫外灯和600 W的可见光灯下光照60 min降解率分别可达到94.5%和55%。     

La2O3/ZnO/TiO2光催化降解活性艳红K-2BP的研究

采用溶胶-凝胶法制备了La₂O₃/ZnO/TiO₂复合光催化剂,以紫外灯为光源,活性艳红K-2BP为模型降解物,研究了La₂O₃/ZnO/TiO₂的光催化性能。结果表明：当锌和镧的掺杂量w(ZnO)=20%, w(La₂O₃)=0.5%, 煅烧温度为500℃时,La₂O₃/ZnO/TiO₂复合光催化剂的光催化活性最高;当催化剂投加量4 g/L,通气量800 mL/min,初始pH值3.12时,La₂O₃/ZnO/TiO₂对活性艳红K-2BP的降解效果最好。实验证明,La₂O₃/ZnO/TiO₂对活性艳红K-2BP的降解遵从Langmuir-Hinshelwood动力学模型,测得其反应速率常数k＝11.5 mg/(L·min);吸附常数K＝2.88×10^-2 L/mg。     

负载型纳米复合半导体WO3-TiO2/AC光催化降解刚果红废水

采用溶胶-凝胶-浸渍-焙烧法制备了负载型纳米复合半导体WO₃-TiO₂/AC光催化剂,以偶氮染料刚果红为目标降解物,通过正交实验优化了刚果红废水的降解条件,并对其光催化动力学进行了探讨。结果表明,刚果红废水的最佳降解条件为：催化剂投加量10 g/L,pH=7,H₂O₂用量为3.5 mL/L。在最佳条件下,当刚果红废水起始浓度为40 mg/L时,反应120 min后,刚果红溶液的去除率可达95.21%,较相同条件下TiO₂/AC对刚果红染料的降解率提高了19.57％。光催化剂对刚果红的光催化降解符合Langmuir-Hinshelwood（L-H）模型。     

六氯苯的O3及UV/O3高级氧化降解试验研究

采用O₃、UV/O₃高级氧化法对水中六氯苯（HCB）的降解效果及机理进行了研究，并对结果进行了比较，结果表明，UV本身对HCB的去除率贡献不大，HCB可被O₃、UV/O₃快速降解，即UV＜O₃＜UV/O₃；O₃、UV/O₃作用时，提高体系的初始pH值不利于HCB的降解，在pH＝3，HCB=0.2 mg/L，反应40 min时，HCB的去除可达50%左右，酸性条件下有利于降解反应的进行；无论是O₃单独作用还是UV/O₃联合作用，HCB的降解基本上满足准一级反应动力学规律，如果体系的pH值基本保持恒定，这种规律就更为明显。根据离子色谱(IC)、GC对六氯苯降解中间产物进行了测定，探讨了O₃、UV/O₃降解六氯苯的途径和机理。     

UV/H2O2/Fe-FeOxH2x-3和UV/H2O2工艺降解水中富里酸的研究

采用硼氢化钠还原法制备核-壳结构的Fe-FeO_xH_2x-3复合材料，研究了富里酸在UV/H₂O₂和UV/H₂O₂/Fe-FeO_xH_2x-3两种不同反应体系下的降解情况。结果表明，核-壳结构Fe-FeO_xH_2x-3的存在，提高了UV/H₂O₂降解富里酸的反应速率，TOC去除达到84%。采用XAD树脂吸附法对反应前后的富里酸进行化学分级表征，结果表明，富里酸经反应后憎水酸（HoA）、弱憎水酸（WHoA）和憎水中性物质（HoN）都有所减少，进而转化为亲水性物质（HiM）；用超滤膜法对富里酸进行物理分级表征，考察了富里酸在反应前后分子量分布的变化情况。同时，富里酸经过反应后生成的中间产物降低了三氯甲烷生成趋势。     

UV/H2O2工艺降解环丙沙星的研究

采用UV/₂O₂工艺去除水体中的喹诺酮类抗生素环丙沙星（CIP）。考察了溶液pH值、₂O₂投加量以及水体基质对环丙沙星降解效率的影响,分析了降解产物的生成情况。研究表明,环丙沙星的降解符合拟一级反应动力学模型。降解速率受溶液pH值的影响,酸性及中性条件,有利于环丙沙星的降解。₂O₂投加量的增大,使得降解速率逐渐增大,但速率增幅逐渐变缓;最佳₂O₂/环丙沙星摩尔比为2 000。实际水体中存在的NOM、NO^-₃,促进了单独UV作用下,环丙沙星的降解。水体中的?OH焠灭剂,抑制了UV/₂O₂联合作用下,环丙沙星的降解;实际水体中的光解速率常数低于超纯水中的光解速率常数。GC-MS分析表明,UV/₂O₂工艺,使环丙沙星氧化降解生成氨基乙酸、丙二酸、丙三醇和对苯二甲酸等小分子有机物。     

Tween-80和H2O2对Burkholderia cepacia降解油脂的影响

油脂废水是一种重要的水污染源。研究了表面活性剂和H₂O₂对洋葱伯克霍尔德氏菌(Burkholderia cepacia)降解油脂的影响。结果表明：适量的表面活性剂和H₂O₂促进油脂的降解。表面活性剂可以增强油脂在水相中的溶解度，提高油脂在水中的乳化程度从而增加其生物可利用性。当Tween-80浓度600mg/L时，油脂降解率达到91%。低浓度H₂O₂不仅能刺激微生物生长，而且使培养液中的pH值保持相对稳定，提高了微生物对油脂的降解率。H₂O₂在浓度为400mg/L时，能使油脂降解率达到90%。     

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)