真空紫外灯动态降解空气中低浓度甲醛的研究

以集中空调中处理室内可挥发性有机物(VOCs)为应用背景,搭建了试验台.实验研究了真空紫外灯(主波长254 nm,185 nm)降解甲醛的影响因素以及产生O3的情况.研究表明,在产生的O3浓度低于室内空气质量标准(0.16mg/m3)的情况下,真空紫外灯也能够高效地降解空气中低浓度甲醛(＜1 mg/m3);甲醛降解率与反应器空气流速及甲醛初始浓度成反比;降解速率与甲醛初始浓度成正比,与反应器空气的流速成反比;绝对湿度对真空紫外灯降解甲醛有一定的影响;反应器空间大小对甲醛降解影响比较显著.应用于集中空调系统净化室内空气中VOCs,取得了很好的效果.     

气-固流化床光催化氧化甲苯的研究

在自制的流化床光催化反应装置中研究了中低浓度（28～140 mg/m^3）甲苯的气相光催化降解过程,考察了光照时间、初始浓度、表观气速和催化剂负载量等因素对甲苯光催化降解率的影响规律.结果表明,紫外灯照射约1.5 h,甲苯的转化率达最大值,甲苯初始浓度越低,维持此最大值的时间越久;在一定低浓度范围内（28～55 mg/m^3）,甲苯的转化率不随浓度变化,符合一级反应动力学,浓度进一步增加,则甲苯的转化率下降;表观气速和催化剂负载量的最佳值分别为3.3Umf和0.19 g TiO2/g SiO2.     

磷钨酸光催化降解甲基橙溶液的研究

以磷钨酸为光催化刺，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300mg／100mL，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。     

新型管状光催化反应器降解VOCs特性

以一种新型折流式管状光催化反应器为研究对象,选择甲醛、苯和甲苯为目标污染物,以紫外光源、催化剂负载量和反应器内循环流量为关键影响因素,利用非密闭型环境舱,分析了反应器降解室内VOCs特性。结果表明,在254 nm和365 nm紫外光源照射下,VOCs的总衰减系数随初始浓度的增加而增大,且254 nm紫外光源照射下的总衰减系数更大。365 nm紫外光源照射时,VOCs的反应有效度随催化剂负载量的增加而增大;254 nm紫外光源照射时,反应有效度受催化剂负载量变化的影响很小。VOCs的转化率随循环流量的增加而增大,而反应速率受循环流量的影响较小;相同的循环流量下,转化率和反应速率均随着VOCs初始浓度增加而增大。由于增设肋片,折流式管状反应器比传统无肋片管状反应器的洁净空气量提升60%,且反应有效度更接近0.5,说明前者的传质-反应速率更加匹配,降解性能明显更优。     

天然沸石负载La2O3-ZnO-TiO2光催化降解活性艳红K-2BP

利用80目天然斜发沸石作载体制备La2O3(0.5%)-ZnO(20%)-TiO2/沸石复合光催化剂,以20 W紫外灯为光源,在自制的光催化反应器中降解活性艳红K-2BP,考察了光照时间、空气通入量、催化剂用量、溶液初始浓度、H2O2与Fe3+投加量等对活性艳红K-2BP光催化降解率的影响。结果表明,当溶液初始浓度为60 mg/L,催化剂投加量为12 g/L,通气量为1 200 mL/min,光照2.5 h,活性艳红K-2BP的降解率可达99.2%;H2O2和Fe3+投加量为4 mL/L和3 g/L时,光照1 h活性艳红K-2BP降解率分别为100%和97.2%。紫外 可见吸收光谱显示,LZTZ光催化剂可有效降解印染废水。     

折流式管状反应器对室内甲醛的净化效果

利用PCO技术,针对现有的室内挥发性有机污染物,设计一种能与建筑空调系统的通风换气设备相结合的折流式管状反应器,以甲醛为目标污染物,对其净化效果进行实验分析。结果表明：折流式管状反应器对于甲醛的降解处理效果高于传统的管状反应器,其转化率及矿化率均大于传统管状反应器;相较于波长较长的黑光灯,波长为254 nm的杀菌灯利用率更高,实验效果优于黑光灯;不同初始浓度下甲醛的反应有效度η基本不受催化层厚度影响;以波长254 nm的杀菌灯为紫外光源时,由于光强衰减快,使得催化层厚度对传质速率无明显作用;以波长为365 nm的黑光灯为紫外灯源时,甲醛η值随催化层厚度增加而增大,故在此实验条件下的光催化反应中,紫外光吸收量、反应速率以及反应有效度均会随催化剂负载量增加而增大。     

固定沼泽红假单胞菌构建悬浮式生物反应器对室内甲醛的去除

利用海藻酸钠及羧甲基纤维素包埋沼泽红假单胞菌海绵作为吸附剂,对甲醛进行吸收处理,其动力学行为与多孔材料相似。用这种海绵组装悬浮式生物反应器,考察其去除室内甲醛污染的性能,结果表明,海绵体积和进风量是影响反应器甲醛净化效率的关键因素。装入6 L海绵和6 L水的反应器在进风量最大(7.8 m3·min-1)时,对室内空气污染浓度为2.0 mg·m-3甲醛的净化效率约为80%。分析水箱水溶液甲醛浓度的变化,结果表明含有甲醛的空气吹入反应器后溶解于水,然后被包埋的光合菌吸收。反应器在污染甲醛浓度为3.5 mg·m-3的试剂室内运行过程中,其甲醛去除率逐渐上升,室内污染甲醛浓度逐渐降低,运行31 d后室内甲醛浓度降为0.04 mg·m-3（低于国标值）,其净化甲醛污染的CADR（clean air delivery rate）值达到481.4 m3·h-1,沼泽红假单胞菌细胞的存活率为98%,说明固定沼泽红假单胞菌具有应用于室内甲醛污染去除的应用潜力。     

O3氧化工艺处理黄连素制药废水研究

采用臭氧（O3）氧化法处理含高浓度黄连素和COD的制药废水,探讨了废水初始pH、O3投加量及初始黄连素浓度等因素对O3氧化过程的影响,确定了O3氧化技术处理黄连素制药废水的最佳操作条件。结果表明,O3能够有效分解废水中的黄连素,降低其COD浓度;黄连素浓度为700mg／L、COD为3500mg／L、pH为0．88的废水,进气O3浓度为14．05mg／（L·min）,处理时间为180rain（即投加量为2529mg／L）时,黄连素和COD的降解率分别可达77．46％和41．28％,BOD,／COD比（B／C比）从0．06提高到0．34,增加了4．7倍;随着废水中初始黄连素浓度的升高,废水COD降解率逐渐降低。O3氧化法是一种有效的黄连素制药废水预处理技术,可以大大提高废水的可生化性。     

雌酮在铁（Ⅲ）-草酸盐配合物体系中的光降解

以125W高压汞灯为光源，研究了水中雌酮（E1）在铁（Ⅲ）-草酸盐体系中的光降解；考察了初始pH值、铁（Ⅲ）／草酸盐配比、E1初始浓度对E1光降解的影响。结果表明，铁（Ⅲ）／草酸盐体系能引发E1的光降解。在pH=3．5，Fe（Ⅲ）／Ox配比为10／120／zmol／L时，2mg／LE1光照160min可以降解59％。在pH3-6范围内，pH为3～4时E1降解效率最高；在2-10mg／L范围内，光降解效率随水溶液中E1初始浓度的增加而降低。     

组合式脉冲电晕反应器处理二氯甲烷废气实验研究

利用线-板和线-筒式串联成组合式脉冲电晕反应器对二氯甲烷(DCM)的降解效果进行了研究,考察了脉冲电源参数、DCM初始浓度、气体流量以及载气等因素对去除效果的影响。结果表明:DCM的去除效果与脉冲高压电源的峰值电压和脉冲频率成正比,与其自身初始浓度和气体流量成反比。在空气作为载气、峰值电压22.5kV、脉冲频率50 Hz、DCM初始质量浓度300mg/m3和气体流量1.2L/min时,DCM的去除率可达到79.5%;傅立叶红外光谱检测可知,主要产物为CO2、N2O、COCl2、CO和H2O等。     

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.     

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.     

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.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

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.