低浓度硫化氢废气的液相催化氧化法净化实验研究

针对H2S浓度为750~1500mg/m3的气体的液相催化氧化技术进行了动力学实验研究。配制了以铁基离子作为主催化剂的复合吸收净化溶液,同时加入稳定剂和表面活性剂提高催化剂在碱性吸收溶液的活性。分别考察了原料气中H2S、O2含量以及吸收液中催化剂离子浓度、温度等因素对吸收速率的影响;确定了较为理想的吸收操作条件并获得了较好的吸收净化效果;饱和吸收液易于再生,净化性能恢复良好,可重复使用。     

低浓度硫化氢废气的液相催化氧化法净化实验研究

针对H2S浓度为750～1500 mg/m^3的气体的液相催化氧化技术进行了动力学实验研究.配制了以铁基离子作为主催化剂的复合吸收净化溶液,同时加入稳定剂和表面活性剂提高催化剂在碱性吸收溶液的活性.分别考察了原料气中H2S、O2含量以及吸收液中催化剂离子浓度、温度等因素对吸收速率的影响;确定了较为理想的吸收操作条件并获得了较好的吸收净化效果;饱和吸收液易于再生,净化性能恢复良好,可重复使用.     

PH3液相催化氧化净化研究

以Mn2 和Pd2 为催化剂的吸收液对含低浓度PH3的混合气进行了液相催化氧化净化研究.考察了催化剂配比、混合气中O2浓度、PH3初始浓度、反应温度、气体流量和吸收液pH与PH3净化效率的关系.结果表明,催化剂中Pd2 与Mn2 的质量比为1:4时可获得较佳的净化效果;随着混合气中O2浓度的增加,吸收液对PH3的净化效率有所提高;在20～75℃内,低温对PH3净化有利,较适宜的反应温度为20℃;较低的PH3初始浓度和低气体流量均有利于PH3的净化;较高的pH有利于吸收液中催化剂催化效能的发挥.吸收液对PH3的净化效率可达100%,但因吸收液中的金属离子易与催化氧化PH3产生的PO3-4形成沉淀,使金属离子脱离液相催化氧化系统,吸收液失效较快.     

膜气体吸收技术分离VOCs/N2混合气性能的研究

以C6H6/N2混合气为代表,疏水性聚丙烯中空纤维膜为气液接触膜,n-甲酰吗啉(NFM,n-formyl morpholine)水溶液为吸收剂,研究了膜气体吸收法分离VOCs/N2混合气性能。考察了吸收剂流量、吸收剂体积分数、进口气流量、进口气浓度和膜组件结构等诸因素对分离性能的影响。结果表明,在吸收剂流量为20～100 mL/min,进口气流量为40～300 mL/min,进口气浓度为10.2 mg/L的条件下,苯的去除率为65.0 % ～ 99.6 %,总体积传质系数为0.0157～0.08412 s-1。实验证明,采用疏水性多孔膜气体吸收法,NFM水溶液吸收分离VOCs/N2混合气具有较高的分离效率和较快的传质速率。     

螺旋切割强化湿法烟气脱硫的传质动力学

针对开发的新型静态螺旋切割强化湿法烟气脱硫技术,根据双膜理论从动力学角度建立了静态螺旋切割强化Ca(OH)2溶液吸收烟气SO2的动力学模型,并采用单因素实验探究了烟气SO2浓度、烟气流量、脱硫剂浓度以及脱硫剂循环流量对传质速率的影响。结果表明：模型能较好地描述静态螺旋切割强化湿法烟气脱硫的实际过程,理论计算与实验数据都发现,烟气SO2浓度、烟气流量、脱硫剂浓度以及脱硫剂循环流量的增加均有助于提高传质速率;但当脱硫剂浓度大于5%时,传质速率随脱硫剂浓度的增加改变不大。     

粉砂介质包气带中甲苯蒸气挥发的迁移转化

挥发性有机物通过包气带向上迁移到地表或室内引发的蒸气入侵(vapor intrusion,VI)问题越发受到关注。以甲苯作为研究对象,采用土柱实验,对粉砂介质包气带中甲苯蒸气发生的扩散、生物降解的规律进行研究。结果表明,粉砂介质中,甲苯蒸气扩散穿透70 cm土柱时间为24 h,甲苯蒸气在土柱内扩散10 d时,土柱达到短暂的稳态平衡;12～30 d时,处于动态平衡;30～60 d时,土柱内甲苯蒸气浓度下降速率发生变化,土柱内O2体积分数下降了8%,CO2体积分数增加了6%;60 d时,甲苯蒸气基本被降解。说明覆盖一定厚度的粉砂对甲苯蒸气的迁移有比较好的阻滞和生物降解作用。     

采用杂多酸化合物溶液同时脱硫脱氮的实验研究

本文对液相催化氧化脱硫脱氮的新方法进行了研究 ,在鼓泡反应发生器内进行了液相催化氧化脱硫脱氮的实验。采用钼硅酸溶液及其还原产物脱除烟气中的SO2 和NOX,分别就吸收液的浓度、pH值、温度、停留时间等因素对SO2 和NOX 去除效率的影响及其变化规律进行了研究。实验结果表明 ,钼硅酸能十分有效地吸收SO2 ,将SO2 氧化成H2 SO4,并使杂多酸还原为杂多蓝。随后又被用于去除NOX,把NOX 还原成N2 ,蓝色溶液再次被氧化成为黄色溶液     

综合利用镁合金废料制氢及氢氧化镁

AZ31B镁合金废片-盐水体系能同时产生氢气和Mg(OH)2,研究了催化剂,Cl-浓度和反应温度对该体系产氢速率的影响,并分析了产物Mg(OH)2的化学成分和形态结构。实验结果表明,与CuCl2相比,铜线作为催化剂不仅产氢的速率高,且不会污染形成的Mg(OH)2。Cl-浓度和反应温度影响对体系产氢速率有较大影响,当温度为60℃,盐水浓度为4 mol/L时产氢速率达到最大值为62 mL/(min·g)。采用扫描电镜、X射线能谱仪表征分析中间产物,探讨Cl-点蚀反应的机理,对产物氢氧化镁粉末进行表征和物相分析的结果表明,产物为高纯度Mg(OH)2纳米材料,其晶体结构和分散性随温度的增加变好,80℃下获得规整的六方晶体。     

Fe-MCM-41催化氧化2,4-二氯苯氧乙酸

采用水热法合成了Fe-MCM-41中孔分子筛,紫外、红外及XRD表征显示铁离子已进入中孔分子筛骨架。以H2O2为氧化剂形成类Fenton试剂,实验结果表明,在催化剂加入量为1 g/L、H2O2体积分数为6%、pH为4、反应时间为10h、反应温度为35℃的条件下,处理质量浓度为50 mg/L的2,4-D废水的降解率达94.95%。宏观动力学研究显示,该反应近似为一级反应,反应速率常数、表观活化能分别为0.21667 min-1和26.65 kJ/mol。     

溶胶-凝胶Ag-Al2O3催化剂还原稀燃氮氧化物的研究

系统地研究了培烧条件、氧气浓度、C／N摩尔比等因素对溶胶-凝胶Ag(5)-Al2O3催化剂活性的影响。实验结果表明,氧气浓度对催化剂活性的影响表现为促进低温活性和抑制高温活性;催化剂的最佳焙烧条件为焙烧温度600℃和升温速率5C／min;催化剂的活性随着C／N摩尔比的降低而降低。此外,还考察了空速对Ag(5)-Al2O3催化剂活性的影响。结果表明,该催化剂在较大的空速范围内具有良好的活性。     

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)