废弃印刷线路板碘化法浸金研究

针对碘化法从废弃印刷线路板中提取金的工艺设计,分别考察了碘的质量分数、n(I₂)/n(I^-)比值、固液比、双氧水的质量分数、pH值、浸出时间和浸出温度对金浸出率的影响。结合正交设计优化实验方法,提出了从废弃印刷线路板中碘化法浸取金的最佳工艺条件：碘的质量分数为1.1％,n(I₂)∶n(I^-)=1∶10,双氧水的质量分数为1.5％,浸出时间4 h,固液比为1∶10,浸出温度为常温（25℃）,溶液pH值为中性,此时金浸出率可达97.5％。     

催化湿式氧化法处理高浓度唑螨酯生产废水的研究

对唑螨酯生产过程中产生的高浓度实际废水采用催化湿式氧化技术在鼓泡式固定床反应器连续反应装置上进行处理。实验表明,制备的复合负载型催化剂CuO-MnO₂-Cr₂O₃/ZrO₂-CeO₂在处理该废水时具有较好的催化活性。通过对反应温度、反应压力、反应空速、气液比和进水pH等工艺条件的考察,得出最佳的工艺条件为：反应温度=220℃,反应压力=5.8 MPa,空速＝1.8 h^-1,V（气）∶V（水）＝260∶1,进水pH＝9,在此条件下COD去除率达到95.2％。     

新型絮凝剂含硼聚硅铝铁的制备和性能研究

向聚硅酸中引入Al³⁺、Fe³⁺、B,制得稳定性更好的高效絮凝剂含硼聚硅铝铁（PFASB）。通过实验得到其最佳配比为：n_(B)/n_(Si)=0.16、n_(Fe)/n_(Al)=0.5 、n_(Al+Fe)/n_(Si)=1。对造纸废水和焦化废水进行混凝实验表明,PFASB的除浊、除COD的能力均优于聚合铝、聚合铝铁和聚硅铝铁,而且矾花产生迅速,矾花粗大密实,是一种性能优异的新型高分子絮凝剂。实验还考察了絮凝剂的形貌和结构,结果表明B、铝及其水解产物、铁及其水解产物和聚硅酸等多种组分之间有相互作用,形成了尺度更大的聚集单元。PFASB的这种特殊结构是其具有良好稳定性和混凝性能的根本原因。     

锰掺杂WO3-TiO2复合光催化剂的制备及其性能研究

溶胶-凝胶和浸渍相结合的方法制备锰掺杂WO₃-TiO₂复合光催化剂，RXD表征，考察WO₃和Mn²⁺掺入量、焙烧温度、焙烧时间及催化剂用量对光催化降解甲基橙的影响。结果表明，500℃焙烧2h，掺杂量n_{（Mn²⁺）}∶n_（WO3）∶n_（TiO2）＝0.8∶1∶100时，光催化活性最高，光催化降解甲基橙溶液，120min后，降解率达90%, 比单纯 TiO₂的光催化活性提高81%。     

超细粉煤灰基成型吸附剂的动态吸附实验

以粉煤灰为原料制备成型吸附剂,对水溶液中亚甲基蓝和Cr⁶⁺进行动态吸附研究,绘制穿透曲线,利用Origin软件对实验数据分析处理,得出穿透曲线的通式C_t=A₁－A₂〖〗1+(t/t₀)^p+A₁。结果表明,初始浓度C₀=25 mg/L,填料高度不同时,达到穿透点的时间随填料高度的增加而增加;填料高度h=200 mm,初始浓度不同时,达到穿透点的时间随初始浓度的增加而减小;该吸附剂对有机染料和重金属离子均有较好的吸附性能;穿透曲线通式的回归线性相关系数表明,该通式可很好地反映超细粉煤灰成型吸附剂的动态吸附过程。     

不同基质共代谢降解2,4,6-三硝基苯酚的研究

以葡萄糖、可溶性淀粉、乙酸钠和苯酚作为共基质,通过35℃恒温生化培养箱缺氧驯化污泥,间歇恒温振荡试验研究了在不同共代谢基质条件下,2,4,6-三硝基苯酚（TNP）的缺氧降解性能。结果表明,经过驯化的微生物加入葡萄糖和苯酚作为碳源,在TNP∶苯酚∶葡萄糖为10∶3∶100的比例下,TNP生物降解率可以从不加碳源时的31.2%提高到86.6%;不同共基质条件下TNP的降解均符合一级反应动力学方程,反应速率常数大小依次是K_苯酚＜K_葡萄糖＜K_{葡萄糖+苯酚},其中葡萄糖和苯酚同时作为共基质时TNP降解速率常数最大为0.019 h^-1。     

污泥的分形维数与粒度随统计样本的变化特征

研究了厌氧折流板反应器(ABR)中成熟颗粒污泥和某污水处理厂回流、厌氧、曝气、消化4个单元中絮状污泥的一维、二维分形维数(D₁、D₂、D′₂)及平均粒径在不同统计样本数下的变化规律。结果表明,当统计样本数达到200以上时,ABR中成熟颗粒污泥的D₁、D₂、D′₂值趋于稳定;当样本数达到300以上时,某污水处理厂4个单元中絮状污泥的D₁、D₂、D′₂值也分别趋于稳定。此外,1^#ABR中的颗粒污泥在统计样本数达到350以上时其中位直径趋于稳定,而2^#ABR和某污水处理厂4个处理单元中的污泥,在试验样本数下并未达到稳定。基于研究的结果和相关文献的结论,研究认为,如果需要得到稳定的平均粒径结果,可能需要大量的统计样本数,该样本数至少要大于600。     

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。     

酚类化合物对硝化颗粒污泥活性抑制的定量结构 活性相关研究

测定了酚类化合物对硝化颗粒污泥活性抑制的logIC₅₀值,以量子化学参数为自变量,应用偏最小二乘法（PLS）,建立了酚类化合物对硝化颗粒污泥活性抑制的定量结构活性相关（QSAR）模型。模型所提取的PLS主成分所能解释的因变量总方差的比例Q²_cum为0.820,表明模型具有较好的稳定性和预测能力。模型的结果表明,影响酚类化合物对硝化颗粒污泥活性抑制的主要因素是logkow、CCR和E_homo,酚类化合物对硝化颗粒污泥活性抑制的logIC₅₀随着分子logkow的增大而减小,随着E_homo和CCR的增大而增大。     

利用给水厂污泥制备透水砖的实验研究

以给水厂污泥、粉煤灰和普通砂为主要原料,添加一定量的粘结剂制备透水砖。探讨了污泥掺加量、烧结温度和成型压力对透水砖基本性能的影响,结果表明,当污泥掺量为30%～40%,添加30%～35%,粒径为1.0～1.4 mm普通砂颗粒时,在30 MP压力下成型、1 150℃下烧结制备出的成品抗压强度达36.53 MP,透水系数为1.08×10-2cm/s,满足JC/T945-2005《透水砖》相关要求。     

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.     

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.     

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.