工业废渣基除磷材料的静态吸附研究

研究了高效除磷材料（EPRC）对磷素的吸附特性,考察了投加量、初始浓度、初始pH值、粒径等对EPRC吸附性能的影响,分析了不同条件下EPRC的吸附过程。结果表明,最佳投加量为3.5 g/250 mL时,去除率达91.07%,出水TP浓度为0.45 mg/L。随着粒径减小,EPRC对磷素的吸附量增大,吸附平衡时间缩短。溶液初始pH值在碱性条件下,吸附容量变大。     

钢渣微粉与混凝剂复合对城市污水处理厂尾水深度除磷的试验研究

针对北方严寒地区低温时生物单元处理效能低下,污水处理厂二级出水TP浓度较高且不稳定的问题,将钢渣微粉与混凝剂复合处理城市污水处理厂尾水,以提高TP的处理效能。研究结果表明,钢渣微粉投加量为4g/L时,其对50mg/L含磷溶液处理效果最佳,处理2h后TP去除率可达75.16%;溶液初始pH对除磷效果有一定影响,最佳初始pH为7～8;小试试验表明,与单独聚合硫酸铁(PFS)混凝沉淀除磷相比,投加4g/L钢渣微粉使PFS最佳投加量由10mg/L降至6mg/L,且TP去除率显著提高,絮体沉降时间缩短,钢渣微粉-PFS絮体沉降2min时絮体体积分数降至10%,远低于PFS絮体。在连续30d的中试运行中,进水TP为1.40～1.98mg/L时,出水TP质量浓度可稳定维持在0.35～0.46mg/L,运行后期pH可降至9以下,满足《城镇污水处理厂污染物排放标准》(GB 18918—2002)一级A排放标准,运行期间药剂成本仅为0.06元/m3,具有一定经济性。     

改性二次锶渣吸附去除废水中的磷

以改性二次锶渣为吸附剂,研究了吸附时间、吸附剂投加量、磷初始浓度和pH值对废水中磷去除效果的影响。结果表明,当总磷浓度为10mg／L,pH为7、二次锶渣投加量为15g／L时,90min内就可使废水中磷的去除率达到95％以上,总磷浓度低于污水综合排放标准的一级标准;改性二次锶渣对磷的吸附符合Langmuir等温吸附模型及准二级动力学模型。     

水枝锦活性炭对孔雀石绿的吸附性能研究

以水枝锦为原料,采用磷酸活化法制备成水枝锦活性炭,通过静态实验研究其对孔雀石绿的吸附性能.考察了水枝锦活性炭投加量、接触时间、pH和孔雀石绿初始浓度对孔雀石绿吸附效果的影响.结果表明,在温度为723 K、活化时间为1 h条件下,水枝锦活性炭得率为36.7%,比表面积为1 223m2/g;在298K、孔雀石绿初始质量浓度为250mg/L、接触270min条件下,水枝锦活性炭的最佳投加量为0.5 g/L,适宜pH为7～12;吸附量随温度的升高而增大,提高温度有利于吸附的进行;水枝锦活性炭静态吸附孔雀石绿的动力学行为符合伪二级动力学方程.静态吸附动力学研究为投加粉状活性炭的吸附池的设计和污水处理装置的运行提供基础信息,对于去除水中孔雀石绿技术的应用具有重要的实际意义.     

矿化垃圾除磷特性及其影响因素的研究

主要研究了KH2PO4溶液在矿化垃圾中的吸附性能,静态和动态试验研究表明在静态试验条件下,初始浓度越高,固液比越小,矿化垃圾吸附磷量越多;pH对磷吸附性能具有较大的影响,当pH在8左右时,矿化垃圾吸磷量达到最大吸附量.在动态实验条件下,湿干比减小,配水速率减小,都有利于矿化垃圾除磷率的增加,当初始溶液的磷质量浓度为50 mg/L时,矿化垃圾有最佳除磷率.     

响应面分析法优化给水污泥吸附除磷工艺

以给水污泥为吸附材料,对模拟含磷废水进行了吸附研究.在单因素实验基础上,选取投加量、pH和粒径3种因素为影响因子,以磷的去除率为响应值,采用Box-Behnken响应面分析法(BBD)研究了3种因素对磷去除率的影响以及各因素间的交互作用.建立了二次多项式回归方程预测模型,成功预测出最佳除磷工艺条件为污泥投加量3.88 g/L,pH=3.00,粒径1.00 mm,该条件下磷的去除率可达95.13％.因此,响应面分析法是优化给水污泥吸附除磷工艺的可行方法.     

多孔陶瓷滤球对杭州西湖沉积物5种形态磷的吸附性能

以新型赤泥基多孔陶瓷滤球(porous ceramic filter material,PCFM)颗粒为吸附剂,采用动态和静态吸附实验相结合的实验方法研究了PCFM颗粒对沉积物磷的吸附性能。动态吸附实验结果表明,影响PCFM颗粒除磷效果的主要因素有投加量、反应时间、上覆水体pH值和环境温度,最佳吸附反应条件为PCFM投加量8 g,反应时间12 h,上覆水体pH=12,环境温度为50℃。静态吸附实验结果表明,随着反应时间的延长,PCFM对沉积物五种形态磷吸附在12 d左右接近或达到了吸附平衡,此时TP、OP、IP、Fe/Al-P和Ca-P的去除量分别为245.89、69.86、155.25、195.22和-49.01 mg·kg-1。可见PCFM对沉积物磷的吸附性能较好,可进一步应用于富营养化湖泊沉积物磷控制。     

硅酸钙微粉吸附预处理焦化废水中COD和NH3-N的实验研究

首次将固体废弃物硅酸钙微粉用于焦化废水的预处理,通过静态和动态吸附实验评价了硅酸钙微粉对COD和NH3-N的去除效果。结果表明:对COD和NH3-N产生吸附作用的有效组分为硅酸钙微粉的水解产物H2SiO3电离产生的HSiO3-和SiO23-;pH通过影响硅酸钙微粉水解反应以及水解产物H2SiO3和有机物、NH3的电离反应来影响去除率。在进水pH=7.00、硅酸钙微粉投加量为170g/L、振荡时间为75min的条件下,静态吸附实验中COD和NH3-N的去除率分别达16.1%和27.1%;经直径为10mm、高度为300mm的硅酸钙吸附柱预处理,动态吸附实验中COD和NH3-N的去除率分别可达58.9%和35.9%。     

磁性水滑石/生物炭复合材料的制备及其对水溶液中磷的吸附性能

以芦苇秸秆生物炭为基体,制备了磁性水滑石/生物炭复合材料(Fe3O4-Mg/Al-LDH/BC)。考察不同pH、Fe3O4-Mg/Al-LDH/BC投加量、初始磷浓度、吸附时间以及反应温度对Fe3O4-Mg/Al-LDH/BC吸附磷的影响。结果表明:Fe3O4-Mg/AlLDH/BC对磷的吸附符合准二级动力学模型和Freundlich模型,吸附过程是自发的吸热反应。在最佳的实验条件下(Fe3O4-Mg/Al-LDH/BC投加量为5.0g/L,磷初始质量浓度为20 mg/L,pH为6.0,温度为30℃,吸附时间为120 min),Fe3O4-Mg/AlLDH/BC对磷的去除率可达99.24%,该材料是一种新型高效的磷吸附材料。     

聚乙烯醇包埋水化硅酸钙粉末制备薄片状材料用于处理含磷废水

采用聚乙烯醇(PVA)包埋固定水化硅酸钙(CSH)粉末,硝酸钠作为交联剂,制备片状除磷材料(PVA-CSH),解决粉状CSH易流失、易堵塞等实用性问题,同时尽量避免对CSH粉末吸附性能的影响。通过SEM和FTIR对材料进行表征,通过批量的静态实验研究材料对含磷废水的吸附行为,通过连续运行实验考察材料的实际应用性能。结果表明,PVA-CSH材料成多孔网状结构,包埋前后CSH基团种类不变;PVA的加入对CSH除磷的吸附速率会有一定的影响,但平衡吸附量基本不受影响,准二级动力学方程可用于描述吸附过程,吸附等温曲线符合Langmuir等温方程;连续柱实验中,同等条件下,CSH及PVA-CSH柱出水磷浓度超出0.5 mg·L~(-1)时,运行时长均为7 d左右,PVA-CSH柱出水COD浓度始终小于10 mg·L~(-1),NO_3~--N浓度始终小于2 mg·L~(-1),PVA-CSH柱出水浊度接近0 NTU显著优于CSH粉末。     

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.     

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.     

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.