PDA的制备及其对水体中邻苯二甲酸二甲酯的去除性能

以二甲基二烯丙基氯化铵(DMDAAC)和丙烯酰胺(AM)为原料,Span-80和Tween-80为乳化剂,液体石蜡为分散相,采用分批加料法,反相乳液聚合制备二甲基二烯丙基氯化铵与丙烯酰胺的共聚物(PDA)。研究内容包括单体配比、引发剂配比、油水体积比和pH值对产物特性粘度的影响。研究获得的优化聚合条件为:单体质量比(DMDAAC∶AM)为2∶8,引发剂质量比(NaHSO3∶K2S2O8)为5∶3,油水体积比为1∶1.2,pH值为8。选用自制PDA用于去除水中邻苯二甲酸二甲酯(DMP)时,在絮凝剂PDA的投加量为0.60 mg/L,pH值为10时,DMP的去除效果最好,去除率达到98.31%。     

浓缩脱水污泥水混凝预处理效果及混凝剂的选择

以白龙港污水处理厂浓缩脱水污泥水为处理对象,考察了聚合氯化铝(PAC)对污泥水颗粒物沉降特性和污染物去除效果的影响,比较了PAC、聚合氯化铁(PFC)、阳离子型聚丙烯酰胺(cPAM)和阴离子型聚丙烯酰胺(aPAM)对浓缩脱水污泥水的预处理效果.实验结果表明,PAC的投加可以去除颗粒态污染物和溶解态的磷,但其形成絮体粒径随PAC投加量增大而减小,导致污泥沉降性能恶化.因此,PAC不适合浓缩脱水污泥水的混凝预处理.与PAC相比,投加PFC、cPAM和aPAM均能有效去除颗粒态污染物,并改善污泥水沉降性能,其中cPAM的预处理效果最佳.     

碳酸根型镁铝水滑石对铬酸根和磷酸根离子的吸附性能

为研究水滑石类材料对水体中铬酸根和磷酸根离子的同时吸附去除性能,采用共沉淀法合成碳酸根型镁铝水滑石(Mg-Al-CO3 LDHs),利用傅立叶转换红外光谱、X射线晶体衍射、表面积、X光吸收近边结构等手段对合成材料进行表征,并研究Mg-Al-CO3 LDHs在不同初始浓度、pH、吸附时间、阴离子干扰条件下同时去除铬酸根和磷酸根离子的性能。结果表明,Mg-Al-CO3 LDHs对铬酸根和磷酸根离子最大吸附量分别为0.042 mmol/g和0.146 mmol/g。吸附动力学实验数据的拟合结果以Elovich为最佳。竞争实验表明,溶液中含有少量磷酸根离子即可抑制铬酸根离子的吸附,但铬酸根离子对磷酸根离子的吸附影响不大。X光吸收近边结构结果表明,铬与构造中心的铝产生键结而吸附。     

高分子絮凝剂SSXA的合成工艺及其在含Cu2+ 废水处理中的应用

以淀粉(ST)、丙烯酰胺(AM)、NaOH、CS2为原料,以硝酸铈铵(CAN)为引发剂合成一种新型的高分子絮凝剂--可溶性淀粉基黄原酸酯-聚丙烯酰胺接枝共聚物(SSXA).以SSXA去除Cu2+性能为依据确定最佳合成条件.结果表明,AM:ST=4:1(摩尔比),ST:NaOH:CS2=2:4:3(摩尔比),黄原酸酯化反...     

两性高分子污泥脱水剂P(AM-DAC-AMPS)的表征与应用

采用三元自由基水溶液聚合法,以丙烯酰胺(AM)、丙烯酰氧乙基三甲基氯化铵(DAC)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为原料,经过复合引发制备了两性高分子脱水剂P(AM-DAC-AMPS),简称为PADA).采用傅里叶变换红外光谱(FT-IR)、透射电镜(TEM)对结构进行了表征,结果证明聚合物为三元共聚物,并具有良好的直链结构.经过PA-DA、CPAM调理后的污泥最佳比阻(r)分别为1.58×109s2/g和1.8×109s2/g,离心后含水率分别为77.4％和78.1％;污泥沉降速度分别为0.3 mL/min和0.25 mL/min;污泥滤液中,多糖去除率分别为70.3％和40.7％,蛋白质去除率分别为31.5％和17.5％;表明PADA比CPAM具有更好的脱水性能.并且通过SEM观察,发现PADA的调理增强了污泥絮体的密实性.     

壳聚糖接枝共聚物的合成及应用研究

在N2保护下,以浓度为0.8 mmol/L硝酸铈铵为引发剂,控制壳聚糖(CTS)和丙烯酰胺(AM)质量比为mCTS∶mAM=1∶6,于50℃下接枝共聚反应3 h,得改性的壳聚糖衍生物(CAM).用IR对产物进行表征.通过对废水的处理,研究了共聚产物在絮凝、COD去除、脱色上的应用.结果表明:CAM的絮凝效果好于聚丙烯酰胺和壳聚糖,CAM对COD的去除率达到84.7%,并有较好的脱色效果.     

新疆油田含油污泥破乳-离心脱水工艺优化

针对新疆油田含油污泥成分复杂、油水分离困难、处理难度大的特性,基于破乳剂、絮凝剂和助剂的油水高效破乳、絮体混凝沉降和助剂骨架强化脱水作用,使用复合调理剂对其进行了处理;并采用响应曲面法研究了破乳剂复配比例、温度、絮凝剂质量浓度对破乳脱水效果的影响。结果表明,各因素影响程度排序为：温度>破乳剂比例>絮凝剂质量浓度。高温有利于污泥脱水的主要原因是,高温有助于降低体系粘度、提升水滴流动性、推动水滴热运动,进而辅助水滴的团聚,最终实现油水分离。在最佳操作条件下(破乳剂NP-9∶SDBS为9∶1且质量浓度为4 g·L⁻¹、温度51 ℃、絮凝剂质量浓度为16 mg·L⁻¹、生石灰加量为1%)进行含油污泥破乳离心分离脱水,脱水率可达92.55%。SEM观察结果表明,复配破乳剂通过改变油泥的堆积方式、增加泥块的疏松程度、增大泥块的孔洞来提高油泥的脱水性能。本研究结果可以为含油污泥减量化处理的现场应用提供参考。     

改性壳聚糖复合凹凸棒土絮凝油漆废水

将壳聚糖、阳离子淀粉和二甲基二烯丙基氯化铵(DMDAAC)进行三元接枝共聚,制备了三元接枝改性壳聚糖(CTS-DMDAAC-CS),通过红外光谱和扫描电镜对其结构进行了表征.并且将三元接枝改性壳聚糖与凹凸棒土进行优化复配,对油漆废水进行了絮凝实验,得出了当pH=12,沉降时间为20 min,复合絮凝剂投加量为0.2 g,三元接枝共聚物:凹凸棒土=1:10时,该复合絮凝剂对油漆去除率最佳能够达到89.3%,并且絮凝效果好,是一种新型绿色环保的有机-无机复合絮凝剂.     

混凝剂中的铝形态对黄河水源水中出水余铝的影响

铝系混凝剂是应用最广泛的无机混凝剂,改善混凝剂中的铝形态可有效提高混凝效果,但其在净水过程中产生的余铝对人体健康及输水过程具有显著的影响。本文研究了氯化铝(AlCl₃)和高聚十三铝(Al₁₃) 2种混凝剂在处理黄河上游水源水时的混凝过程,结合出水中的溶解态及不同分子质量余铝含量、有机物紫外吸光度(UV₂₅₄)、pH、浊度、有机物种类及含量和絮体特性的变化趋势,探究混凝剂中的铝形态对混凝过程的影响。结果表明,在实验投加量范围内,当Al₁₃做混凝剂时,出水余铝质量浓度均低于0.2 mg·L⁻¹。Al₁₃具有较高的形态稳定性,在混凝过程中对出水pH影响较小。絮体粒度随混凝剂投加量的增加而增加,Al₁₃投加量达到0.08 mmol·L⁻¹时絮体粒度下降(强度因子由于静电排斥作用而下降)。在不同投加量下,使用AlCl₃做混凝剂时出水余铝均高于Al₁₃体系,且在不同投加量下AlCl₃体系出水余铝中小于1 000 Da的余铝占比最大。Al₁₃对富里酸和腐殖酸的去除效果优于AlCl₃,且AlCl₃在较高投加量下才能实现水中有机物的有效去除。     

含油污泥清洗剂的制备与研究

以异丙醇为溶剂,偶氮二异丁腈(AIBN)为引发剂,甲基丙烯酸(MAA)、丙烯酸丁酯(BA)和苯乙烯(St)为混合单体,通过溶液聚合的方法制备一种含油污泥清洗剂.介绍了该清洗剂的制备方法,考察了单体用量及清洗条件对清洗剂脱油性能的影响,探讨了清洗剂对含油污泥中原油不同组分的去除效率,并用红外光谱证实了所制备共聚物结构的官能团.清洗剂性能评价表明:单体用量和清洗条件均有最佳值,其中单体最佳质量比为MAA:BA:St=21:62:17,最佳清洗条件分别是:加药浓度为250 mg/L,水洗温度为60℃,反应时间为40 min;清洗剂对含油污泥中芳烃去除率最高,达93.0%.     

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.