水体中常见无机阴离子对TiO2薄膜光催化降解甲醛的影响

选择了5种水体中常见的阴离子(Cl^-,SO^2-₄,HPO^2-₄/HPO^2-₄,HCO^-₃/CO^2-₃和NO^-₃),分别考查了其对TiO₂薄膜光催化降解模拟甲醛废水的反应速率的影响;从上述离子的光吸收,对·OH的捕获及其生成的相应的无机自由基的氧化作用以及与甲醛的竞争吸附3个方面讨论了上述离子影响TiO₂薄膜光催化降解模拟甲醛废水的反应速率的原因。结果表明,HCO^-₃/CO^2-₃对TiO₂薄膜光催化降解甲醛具有抑制作用,Cl^-和SO^2-₄的影响不大,H₂PO^-₄/HPO^2-₄和NO^-₃具有促进作用。造成上述结果的主要原因是HCO^-₃/CO^2-₃具有很强的·OH捕获作用;Cl^-,SO^2-₄对·OH捕获作用以及竞争吸附都较弱;H₂PO^-₄/HPO^2-₄在TiO₂表面具有较强的吸附能力,释放出的H⁺起到了酸催化剂的作用;NO^-₃在紫外光的照射下可以产生·OH,此外NO^-₃作为电子受体而降低了TiO₂表面光生电子和空穴的复合几率。     

原位水解生成的羟基氧化铁凝聚吸附除磷效能与机制简

将不同摩尔比Fe³⁺与OH^-（[Fe³⁺]：[OH^-]=1：0、1：1、1：2和1：3）反应获得原位水解生成的羟基氧化铁（in situ FeO_xH_y）,研究了具有不同水解程度的羟基氧化铁对凝聚吸附除磷效能与机制。研究显示,In situ FeO_xH_y对磷的去除率随铁投量增大而升高,且均在中性pH范围内具有最佳除磷效果;在相同铁投量条件下,磷去除率随着[OH^-]：[Fe³⁺]的升高而降低;当体系碱度较低时（pH<6）,引入OH^-可促进Fe³⁺水解而提高除磷效果。4种羟基氧化铁均可在15 s内可快速吸附磷,且吸附过程符合准二级动力学模型;Freundlich模型均可很好地描述磷在4种羟基氧化铁表面的吸附行为。磷酸盐吸附后,In situ FeO_xH_y表面Zeta电位明显降低,且[Fe³⁺]：[OH^-]为1：0的羟基氧化铁降低最为显著。结合MINITEQ计算软件磷酸盐、铁盐形态分析结果显示,对于碱度较低的体系,通过投加一定量OH^-可促进Fe³⁺水解,进而使得其更易与水中H₂PO₄^-与HPO₄^2-结合,生成具有多核羟基的磷酸铁络合物,进而提高除磷效果。     

悬浮填料生物塔净化低浓度氮氧化物废气研究

采用多孔球型悬浮填料挂膜的生物塔净化低浓度氮氧化物废气的研究结果表明,氮氧化物的净化效率可达60%,适宜的入口NOx浓度为130 mg/m³,O₂体积含量为18%,空床停留时间为29 s,循环液流量为116.8 L/h, 循环液pH为7.49~8.05,压降为244.9 Pa,温度为22~28 ℃。NO^-₃和NO^-₂浓度相近的现象说明反硝化细菌存在,并发挥着反硝化作用,将部分NO^-₃转化为NO^-₂。     

UASB反应器厌氧氨氧化菌的脱氮特性研究

研究UASB厌氧氨氧化（ANAMMOX）反应器运行情况,采用普通城市污水厂活性污泥接种,人工合成废水,pH值在7.4～7.8之间,温度控制在(32±1)℃。在反应器稳定运行270～450 d之间的180 d中,对NH⁺₄-N和NO^-₂-N去除率均达到99.9％以上,总氮去除率保持在90％以上,NO^-₃-N产生量在20～30 mg/L之间波动。研究表明,UASB厌氧氨氧化反应器处理废水效果明显,对NH⁺₄-N、NO^-₂-N和TN去除率高,NO^-₂-N和NH⁺₄-N比值可以指示厌氧氨氧化反应器性能的演变。UASB反应器稳定运行阶段容积负荷的影响较小,ANAMMOX菌对合成废水适应性强,反应器抗冲击能力较强,受冲击后恢复迅速。出水pH值稳定在8.5附近,pH值变化情况可作为反应器运行状况的指示。关键词硝化厌氧氨氧化上流式厌氧污泥床生物脱氮     

氨吹脱-Fenton氧化预处理阿奇霉素废水的研究

采用氨吹脱-Fenton试剂氧化法对阿奇霉素废水进行预处理,考察了各种因素对处理效果的影响。实验结果表明：在pH值为11,吹脱时间160 min,温度30℃的条件下,氨氮浓度从2 458.7 mg/L降低到421.7 mg/L,去除率可达82.85%;Fenton氧化吹脱出水的适宜工艺条件：初始pH值为3、反应时间90 min、FeSO₄·7H₂O投加量为0.01 mol/L、H₂O₂/Fe²⁺的投加比16∶1,此时,COD去除率为72.6%;废水经预处理后,有效地改善了废水水质,提高了废水的可生化性,由初始的0.1增至0.37,为后续废水的生化处理提供了有利条件。     

污泥回流分离工艺（RSSP）除磷脱氮试验研究

介绍了一种新型的脱氮除磷工艺——回流污泥分离工艺（return sludge separate process）,及其运行情况。该工艺在传统的厌氧缺氧好氧（A²/O）的模式下,针对硝酸盐对厌氧释磷的抑制问题进行改进,提出回流污泥的气浮浓缩分离方案,以提高系统的脱氮除磷效果。研究结果表明,在进水COD为250～400 mg/L,NH⁺₄-N为30～45 mg/L,PO^3-₄-P为8～10 mg/L左右时,该工艺对NH⁺₄-N和PO^3-₄-P的去除率分别可达79.3%和95%。该系统与A²/O的平行比较数据表明,该系统能够提高氮磷综合处理效率,解决A²/O处理工艺中存在无效释磷和硝酸根抑制问题。     

短程硝化过程中NO-2-N高效富集的工艺条件实验研究

针对厌氧氨氧化工艺需要提供充足的亚硝酸盐氮为电子受体的问题,利用培养基对SBR中具有一定短程硝化功能的污泥进行富集培养,得到氨氧化菌和亚硝酸盐氧化菌的数量之比为104︰1,并研究了工艺条件对短程硝化的影响,结果表明,适合氨氧化菌生长的最佳温度为30℃、pH为7.5、nHCO^-₃/nNH⁺₄-N值为1。以适合氨氧化菌生长的最佳环境条件优化SBR,在进水氨氮浓度为250 mg/L时,氨氮的转化率达到90％以上,亚硝酸盐氮积累率维持在85％以上,反应器中氨氧化菌与亚硝酸盐氧化菌的数量之比为10³∶1,亚硝酸盐的高效积累为厌氧氨氧化工艺处理高氨废水的过程提供了稳定的电子受体。     

几种阴阳离子对磷钨酸光催化降解甲基橙的影响

以磷钨酸为光催化剂,在紫外灯照射下,对甲基橙溶液进行光催化降解,考察了几种阴阳离子对磷钨酸光催化降解甲基橙溶液的影响。结果表明：Mg²⁺、Ca²⁺、NO^-₃、SO^2-₄和CO^2-₃均对催化活性有促进作用,其中Mg²⁺和Ca²⁺仅有微弱的促进作用;NO^-₃和SO^2-₄随着浓度的增加促进作用也有所增加;CO^2-₃则随着浓度的增加促进作用呈下降趋势;Mn²⁺、Al³⁺和Cl^-对光解反应存在较强的抑制作用,且Al³⁺和Cl^-随着其浓度的增加,抑制作用增强。     

混合固定化硝化菌和好氧反硝化菌处理焦化废水

对传统的聚乙烯醇(PVA)固定化方法进行了改进,试制了加入麦秸粉末的固定化球和以活性炭纤维膜为载体膜固定化细胞产品。混合固定化硝化细菌和好氧反硝化细菌对经过厌氧折流板反应器酸化后的焦化废水进行脱氮,焦化废水在厌氧折流板反应器中经过18 h的酸化后,pH在8.0左右,开始进入好氧槽进行脱氮。在有效容积为5 L好氧槽中经过12 h的曝气处理,加入麦秸粉末的固定化球对氨氮的去除率高达94.3%;纤维膜固定化细胞产品对氨氮的去除率为85%。整个脱氮过程无NO^-₂-N和NO^-₂-N的积累,实现了好氧条件下的同时硝化和反硝化。     

水位波动带氮素迁移转化规律

为考察水位波动对非饱和-饱和土层中氮素迁移转化的影响,设计土柱实验装置Ⅰ和Ⅱ分别模拟水位稳定与波动两种情景,测定一个水位波动周期内地下水中NO₃^--N、NO₂^--N和NH₄⁺-N浓度变化情况。结果表明,柱Ⅱ水位第1次下降柱内1^#,2^#,3^#,4^#采样点NO₃^--N浓度均增大,增幅分别为6.5%、14.9%、15.33%和19.8%。水位上升时结果相反,分别降低17.3%、26.15%、50.29%和44.61%。第2次水位下降至初始位置4个采样点NO₃^--N浓度再次增大,幅度分别为7.1%、10.6%、13.89%和7.76%。铵态氮呈相反趋势不同程度的变化。水位波动柱Ⅱ连通水槽内总氮量增加显著高于柱I水槽,即水位波动有利于波动带地下水中氮素垂向迁移,加重波动带以下地下水硝酸盐污染。因此,水位波动对氮素迁移转化的影响不容忽视。     

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.     

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.     

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.     

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.     

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.